It is well known, of course, that one may impart color to thermoplastic polymeric compositions by using pigments and soluble dyes. See, for example, Coloring of Plastics, T. G. Weber, ed., John Wiley & Sons, New York, 1979. Plastics colored with pigments are usually opaque and may lack brilliance of color afforded by soluble dyes. Use of pigments also is accompanied by problems in storage, blending, uniformity, etc. Some of the deficiencies encountered in the use of pigments can be overcome by use of soluble dyes which give improved clarity and brilliance, but this approach often results in migration and problems related to solvent extraction of the dye from the thermoplastic resins. Some improvement in solvent extraction and migration properties has been achieved by incorporating poly(oxyalkylene) polymer units into colorants. (See U.S. Pat. No. 4,640,690.) These colorants have the disadvantage, however, of having a significant portion of their weight consisting of non-colored polymeric composition. U.S. Pat. No. 4,116,923 teaches the incorporation of reactive colorants into cross-linked polyester resins and the use of these colored polyester resins to color thermoplastics such as polyolefins. Here again, a major portion of the colored polyester resin used to color the polyolefins is "non-colored" resulting in lower tinctorial strength. Finally, it is known that one may improve the nonextractability of colorants and UV absorbers in thermoplastic polyesters by copolymerizing thermally stable colorants into the backbone of the polyester composition. (See U.S. Pat. Nos. 4,617,373; 4,617,374; and 4,707,537.) This method suffers from the difficulty in finding non-volatile, very reactive colorants which will not be lost by volatilization or decomposition during the stages of ester interchange and polycondensation of the polyester preparation.
West German Patent No. 1,088,637 describes high molecular weight pigment dyes which are derived from aromatic dialdehydes and bifunctional active methylene compounds. These compounds are described as useful as colored pigments in the fields of plastics, paints and printing inks. The polymeric colorants of the present invention, as described below, can be utilized as soluble colorants for thermoplastic resins and have increased light absorbing capability relative the high molecular weight pigment dyes.
It is known that one may color thermoplastic polymeric materials using color concentrates consisting of physical admixtures of polymers and colorants. However, the use of such physical admixtures to color polymeric materials such as polyesters, e.g., poly(ethylene terephthalate) and blends thereof, presents a number of problems:
1. Colorant migration during drying of the colored polymer pellets. PA1 2. Colorant migration during extrusion and colorant accumulation on dies which can cause film rupture and shut-downs for clean-up, etc. Such colorant migration and accumulation result in time consuming and difficult clean-up when a polymer of another color is subsequently processed in the same equipment. PA1 3. Colorants may not mix well, for example, when using two or more color concentrates to obtain a particular shade. PA1 4. Colorants may diffuse or exude during storage of the colored polymeric material. PA1 X is selected from cyano; unsubstituted and substituted carboxylic acid ester; unsubstituted and substituted carbamoyl; unsubstituted or substituted alkylsulfonyl; C.sub.3 -C.sub.8 cycloalkylsulfonyl; or arylsulfonyl or unsubstituted or substituted carbocylic or heterocyclic aryl; PA1 Y is selected from --O--, --S--, --NH-- or substituted imino; PA1 Z.sup.- is a counter anion; R is hydrogen, lower alkyl, or unsubstituted or substituted carbocyclic or heterocyclic aryl; PA1 R.sub.1 is selected from hydrogen or 1-2 groups selected from lower alkyl, lower alkoxy or halogen; PA1 R.sub.2 is selected from hydrogen, unsubstituted or substituted lower alkyl, C.sub.3 -C.sub.8 cycloalkyl or unsubstituted or substituted carbocyclic or heterocyclic aryl; PA1 R.sub.2 ' is selected from --OR.sub.3, --NHR.sub.3, or one of the groups listed for R.sub.2 ; PA1 R.sub.3 is unsubstituted or substituted alkyl; C.sub.3 -C.sub.8 cycloalkyl or unsubstituted carbocyclic or heterocyclic aryl; PA1 or wherein .dbd.A--L.sub.1 --A.dbd. in combination has the structure .dbd.C(CN)-arylene-C(CN).dbd.; PA1 and wherein the divalent moiety B is represented by one of the following formulae: ##STR4## wherein R.sub.4 and R.sub.10 are hydrogen or 1-2 substituents selected from lower alkyl, lower alkoxy or halogen; PA1 R.sub.5 and R.sub.12 are selected from unsubstituted lower alkyl, lower alkenyl, lower alkynyl, C.sub.3 -C.sub.8 cycloalkyl, or phenyl and substituted lower alkyl, C.sub.3 -C.sub.8 cycloalkyl and phenyl; PA1 R.sub.6 is selected from unsubstituted or substituted lower alkylene, C.sub.3 -C.sub.8 cycloalkylene, arylene, alkylene-arylene-alkylene, alkylene-(C.sub.3 -C.sub.8)cycloalkylene-alkylene, alkylene-O-alkylene, alkylene-S-alkylene, alkylene-SO.sub.2 -alkylene, alkylene-O-arylene-O-alkylene, alkylene-N(SO.sub.2 R.sub.3)alkylene or alkylene-arylene; PA1 R.sub.7, R.sub.8, R.sub.9 are hydrogen or alkyl; PA1 R.sub.11 is hydrogen, lower alkyl or aryl; PA1 R.sub.13 is selected from lower alkylene, --O--R.sub.6 -- or --N(SO.sub.2 R.sub.3)--R.sub.6 --; PA1 L.sub.1 is selected from the same divalent groups as listed above for R.sub.6 ; PA1 L.sub.2 is selected from a covalent bond; unsubstituted or substituted phenylene; C.sub.3 -C.sub.8 cycloalkylene; --O--; --S--; --SO.sub.2 --; --CO--; --CO.sub.2 --; --OCO.sub.2 --; --O.sub.2 C-alkylene-CO.sub.2 --; --O.sub.2 C-arylene-CO.sub.2 --; --O.sub.2 C--(C.sub.3 -C.sub.8)cycloalkylene-CO.sub.2 --; --O.sub.2 CNH-alkylene-NHCO.sub.2 --; --O.sub.2 CNH-arylene-NHCO.sub.2 --; --CO.sub.2 -alkylene-O.sub.2 C--; --SO.sub.2 N(R.sub.2)--; --N(R.sub.3)--; --SO.sub.2 -alkylene-SO.sub.2 --; --SO.sub.2 -arylene-SO.sub.2 --; --SO.sub.2 N(R.sub.2)-alkylene-N(R.sub.2)SO.sub.2 --; --SO.sub.2 N(R.sub.2)-arylene-N(R.sub.2)SO.sub.2 --; --O-alkylene-O-- or --O-arylene-O--; PA1 L.sub.3 is selected from covalent bond, --O--, --CH.sub.2 -- or --CH(CH.sub.3)--; PA1 and n is an integer of from 2 to about 50; or --B--L.sub.2 --B-- in combination represents the formula: ##STR5## wherein L.sub.4 is selected from --N(R.sub.5)--, --O--, --S--, --CH.dbd.CH-- or ##STR6## PA1 R.sub.4 ' is selected from the groups listed for R.sub.4 ; PA1 R.sub.5 is selected from the following groups: lower alkenyl; cycloalkyl; cycloalkyl substituted with one or two of lower alkyl, lower alkoxy or halogen; phenyl and phenyl substituted with one or two of lower alkyl, lower alkoxy, alkoxycarbonyl, halogen, alkanoylamino, cyano, nitro or alkylsulfonyl; straight or branched chain alkyl of 1-8 carbons and such alkyl substituted with one or more of the following: C.sub.3 -C.sub.8 cycloalkyl and C.sub.3 -C.sub.8 cycloalkyl substituted with one or two of lower alkyl, lower alkoxy, or halogen; phenyl and phenyl substituted with one or more of lower alkyl, lower alkoxy, alkoxycarbonyl, halogen, alkanoylamino, cyano, nitro or alkylsulfonyl; cyano; halogen; 2-pyrrolidino; phthalimidino, vinylsulfonyl; acrylamido; o-benzoic sulfimido; alkoxy; alkoxy alkoxy; cyanoalkoxy; phenoxy; phenoxy substituted with lower alkyl, lower alkoxy, or halogen; groups of the formula: ##STR9## wherein Y.sup.1 is selected from o-phenylene; o-phenylene substituted with lower alkyl, lower alkoxy, halogen or nitro; --O--CH.sub.2 --; --OCH.sub.2 CH.sub.2 --; --CH.sub.2 OCH.sub.2 --; --S--CH.sub.2 ; --CH.sub.2 SCH.sub.2 --; --NHCH.sub.2 --; --NHCH.sub.2 CH.sub.2 --; --N(alkyl)CH.sub.2 --; --N(alkyl)CH.sub.2 CH.sub.2 -- or --NHC(C.sub.6 H.sub.5).sub.2 --; groups of the formula: ##STR10## wherein R.sub.14 is selected from lower alkyl; cycloalkyl; phenyl; phenyl substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen; pyridyl; pyrimidinyl; benzoxazolyl; benzothiazolyl; benzimidazolyl; 1,3,4-thiadiazolyl, 1,3,4-oxadiazolyl; these heterocyclic radicals substituted with one or more groups selected from lower alkyl, lower alkoxy or halogen; PA1 R.sub.15 is selected from hydrogen, lower alkyl or benzyl; wherein the alkyl groups represented by R.sub.5 may be further substituted by groups of the formulae: EQU --SO.sub.2 R.sub.16 ; EQU --SO.sub.2 N(R.sub.17)R.sub.18 ; EQU --CON(R.sub.17)R.sub.18 ; EQU R(R.sub.17)COR.sub.18 PA1 R.sub.16 is selected from cycloalkyl; cycloalkyl substituted with alkyl; allyl; phenyl; phenyl substituted with one or two groups selected from lower alkyl, lower alkoxy or halogen; lower alkyl; lower alkyl substituted with one or more groups selected from lower alkoxy, halogen, cyano, C.sub.3 -C.sub.8 cycloalkyl, phenyl, phenoxy, alkylthio or alkylsulfonyl; PA1 R.sub.17 and R.sub.18 are each independently selected from hydrogen or those groups represented by R.sub.16 ; PA1 R.sub.6 is selected from lower alkylene, alkylene-O-alkylene or alkylene-S-alkylene; PA1 L.sub.1 is selected from lower alkylene, alkylene-O-alkylene, alkylene-(C.sub.3 -C.sub.8)cycloalkylene-alkylene, alkylene-phenylene-alkylene, alkylene-S-alkylene or C.sub.3 -C.sub.8 cycloalkylene; and PA1 L.sub.2 is selected from a covalent bond, phenylene, C.sub.3 -C.sub.8 cycloalkylene, --O--, --S--, --SO.sub.2 --, --O.sub.2 C-alkylene-CO.sub.2 -- or --O.sub.2 C-arylene-CO.sub.2 --.